Chemical manufacture



Patented Mar. 7, 1950 2,499,368 CHEMICAL MANUFACTURE Melvin De Groote,University City, and Bernhard Kaiser,

Webster Groves, Mo.,

assignors to Petrolite Corporation, Ltd, Wilmington, 1301., acorporation of Delaware No Drawing. Application February 16, 1948,Serial No. 8,726. In Venezuela March 7, 1947 This invention relates toprocesses or procedures particularly adapted for preventing, breaking,or resolving emulsions of the water-inoil type, and particularlypetroleum emulsions. This application is in part a continuation ofcopending applications, Serial Nos. 518,660 and 518,661, both filedJanuary 17, 1944; Serial Nos. 666,817 and 666,821, both filed May 2,1946; as well as Serial Nos. 666,818 and 666,816, both of which werealso filed May 2, 1946; Serial Nos. 727,282 and 727,283, both filedFebruary 7, 1947; and Serial No. 751,610 filed May 31, 1947, all nowabandoned.

New chemical products or compounds, as well as the application of suchchemical compounds, products, and the like, in various other arts andindustries, along with methods for manufacturing said new chemicalproducts or compounds which are of outstanding value in demulsification,described herein, are described and claimed in our co-pendingapplication, Serial No. 751,623 filed May 31, 1947 (now abandoned), andalso our copending application, Serial No. 8,727 filed February 16,1948.

Our invention provides an economical and rapid process for resolvingpetroleum emulsions of the water-in-oil type that are commonly referredto as cut oil, roily oil, emulsified oil, etc., and which comprise finedroplets of naturallyoccurring waters or brines dispersed in a more orless permanent state throughout the oil which constitutes the continuousphase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively soft waters or weakbrines. Controlled emulsification and subsequent demulsification underthe conditions just mentioned are of significant value in removingimpurities, particularly inorganic salts from pipeline oil.

Demulsification as contemplated in the present application includes thepreventive step of commingling the demulsifier with the aqueouscomponent which would or might subsequently become either phase of theemulsion in the absence of such precautionary measure. Similarly, suchdemulsifier may be mixed with the hydrocarbon component.

In our co-pending applications above referred to we have describedcertain new products or compositions of matter which are of unusualvalue in certain industrial applications requiring the use of productsor compounds showing surface activity. We have found that ifsolvent-soluble 21 Claims. (Cl. 252--331) resins are prepared fromdifunctional (direactive) phenols in which one of the reactive (0 or p)positions of the phenol is substituted by a hydrocarbon radical havingnot over 24 carbon atoms, in the substantial absence of trifunctionalphe- 'nols, and aldehydes having not over 8 carbon atoms, subsequentoxyalkylation, and specifically.

oxyethylatiomyields products of unusual value for demulsificationpurposes provided that oxyalkylation is continued to the degree thathydrophile properties are imparted to the compound. By substantialabsence of trifunctional phenols, we mean that such materials may bepresent only in amounts so small that they do not interfere with theformation of a solvent-solubl resin product and, especially, of ahydrophile oxyalkylated derivative thereof. Theactual amounts to betolerated will, of course, vary with the nature of the other componentsof the system; but in general the proportion of trifunctional phenolswhich is tolerable in the conventional resinification proceduresillustrated herein is quite small. In experiments following conventionalprocedure using an acid catalyst in which we have included trifunctionalphenols in amounts of from 3% to about 1% or somewhat less, based on thedifunctional phenols, we have encountered difficulties in preparingoxyalkylated derivatives of the type useful in the practice of thisinvention.

Attention is directed to six co-pending applications (now abandoned):

(1) In respect to the use of demulsifying agents of the kind abovedescribed with the proviso that the hydrocarbon substituent in thephenolic nucleus has 4 to 8 carbon atoms, we refer to our co-pendingapplication for patent, Serial No. 727,282 filed February 7, 1947.

(2) In respect to the same products as new compositions or as newproducts valuable for various purposes in addition to demulsification,attention is directed to our co-pending application, Serial 751,619filed May 31, 1947.

(3) In respect to the use of demulsifying agents of the kind abovedescribed with the proviso that the hydrocarbon substituent in thephenolic nucleus has 9 to 18 carbon atoms, we refer to our co-pendingapplication, Serial No, 751,608 filed May 31, 1947.

(4) In respect to the same products as new compositions or as newproducts valuable for various purposes in addition to demulsification,attention is directed to our co-pending application, Serial No. 751,618filed May 31, 1947.

(5) In respect to the use of demulsifying agents 3 of the kinddescribed, with the proviso that the hydrocarbon substituent in thephenolic nucleus has at least 2 and not more than 3 carbon atoms, werefer to our co-pending application for patent, Serial No. 751,606 filedMay 31, 1947.

(6) In'respect to the same products as new compositions or as newproducts valuable for various purposes in addition to demulsification,attention is directed to our co-pending application, Serial No. 751,617filed May 31, 1947.

Attention is also directed to our oo-pending applications, Serial No.751,605filedMay'31, 1947, and Serial No. 751,620 filed May 31, 1947,both now abandoned. These applications are concerned With oxyalkylatedresins as such or their use as demulsifiers where the hydrocarbonsubstituent in the phenolic nucleus has 2 to-24 carbon atoms.

The oxyalkylated derivatives used in the practice of the presentinvention are rarely a single compound but almost invariably are amixture of cogeners. One'useful'type of compound may be exemplified inanidealized simplification in the following formula:

R it

R R n" R In these formulasn" represents anumeral varying from 1 to 13 oreven more provided thatthe parent resin is fusible and organicsolvent-soluble; n represents a numeral varying from :1 to 20 with theproviso that the average value of n be at least 2; and R is ahydrocarbon radical having not over 24 carbon atoms. These numericalvalues n and n" are, of course, on a statistical basis.

The present invention involves the use, as a demulsifier, of ahydrophile oxyalkylated 2, 4, 6 (i. e., 2, 4 or 6) C1- to 024-hydrocarbon substituted monocyclic phenol-'C1 to "Ca aldehyde resin inwhich the ratio of oxyalkylene groups to phenolic nuclei is at least 2:1and the alkylene'radicals of the oxyalkylene groups are'ethylene,propylene, butylene, hydroxy propylene or hydroxy butylene correspondingto the alpha-beta alkylene oxides, ethylene oxide, alpha-beta propyleneoxide, alpha-beta butylene oxide, glycide and methylglycide.

One may employ mixtures inwhich the various classes of materials appear,particularly admixtures including a cresol, all of which will beillustrated by subsequent examples. More particular1y,"the presentinvention involves the use,.

as a demulsifier, of a compound having the following characteristics:

(l) Essentially a polymer, probablyilinear but not necessarily so,having at least 3 and preferably not over 15 or 20 phenolic'orstructural units. It mayhave more, as previously stated.

(2) The parent resin polymer being fusible and organic solvent-solubleas hereinafter described.

(3) The parent resin-polymer being free from .the phenolic hydroxylposition except possibly in an exceptional instance Where a stablemethylol group has been formed by virtue of resin .manufacture inpresence of an alkaline catalyst. Such occurrence of a stable methylolradical is the exception rather than the rule, and

in any event apparently does not occur when the resin is manufactured inthe presence of an acid catalyst.

5) The total number of alkyleneoxy radicals introduced must be at .leastequal to twice the phenolic nuclei.

(6) The. number .of :alkyleneoxy radicalsv introduced .:not only:mustmeet the minimum of item (-5) above but ;a1so'must besufdcient toendow the product with sufficient hydrophile property to haveemulsifying properties, :or be self-emulsifiable 101' self-.dispersible,:or the equivalent as hereinafter described. The invention is concernedparticularly with ?the use of sub-surfaceactive and surface-activecompounds.

(7') The use :ofaproduct derived from aparasubstituted phenolisadvantageous as compared with the use of a product derivedfrom1an-orthosubstituted phenol, when both are available. Thispreference :is :based, "not :only on the fact that the para-substitutedphenol is usually oheaper,.but also where-we. have been able tosmake acomparison .it appears to be definitely better in the effectiveness :of.demulsifiers.

We have found L when a oxyalkylated derivatives are obtainedconformingto the above specifications, particularly in light-of what issaid hereinafter in greater detail,".that'they;have unusual propertieswhich can be better understood perhaps in :light of the. following:

('a) .Thepropefity isnot uniformly inherent in every analogous structurefor thereason :that if the imethylene group is replaced by sulfur, forexample, we have iiound ,such compounds to .be of lesser :value.

.01) Similarly, the property is not uniformly inherent in everyanalogous structure for the reason that if .R replaced :by::some.oth'er'substituent, :for .instance, rchlorine, the compounds obtainedare'of reduceduvalue in comparison with compounds obtained fromparaeethylphenol 'or propylphenol, .or ortho-ethylphenol ororthopropylphenol. On the other lhand,'the products obtained .fromphenolswhereR'represents 2 carbon atoms or'3 carbon atoms are of,reduced value for demulsificatio-n, in comparison with compoundsderived, ;for example, from difunctional butylphenol, difunctionalamylphenol, diiunctional 'octylphenol, difunctional' nonylphenol,difunctional 'decylphenol, difunctional :menthylphenol,.etc. Derivativesof ortho'.or;paracresol are of reduced value as compared .to derivativesofrdifunctional ethyl or propyl phenols.

(c) We know of no theoretical explanation .of the unusualpro-pertiesof'thisparticular class of compounds andcasamatter of fact, We have notbeen ablelto find a-satisfa'ctory. explanation even after we :haveprepared and studied several hundredatypical compounds.

We have also found that the remarkable 'aieases leum emulsions of thewater-in-oil type by means I of certain specified demulsifiers. Thespecified demulsifiers are the products obtained by the oxyalkylation ofcertain resins, which in turn are derived by chemical reaction betweendifunctional monohydric phenols and a reactive aldehyde such asformaldehyde, nearby homologues, and their equivalents. The phenolicreactant is characterized by one ortho-para nuclear hydrocarbonsubstituent having not over 24 carbon atoms. Usually the phenolicreactants are derivatives of hydroxybenzene, i. e., ordinary phenol, andare usually obtained by reaction of phenol with an olefin or an organicchloride in presence of a metallic halide or condensing agent, butsimilar phenolic reactants obtained from metacresol or 3,5-xylenol areequally satisfactory for the reason that such phenols are stilldifunctional (direactive) and the presence of the single or even bothmethyl radicals does not materially affect the subsurface-activity orthe surface-activity or hydrophile balance. The hydrocarbon substituenthaving not over 24 carbon atoms may be alkyl, alkylene, aryl, alicyclicor aralkyl.

Any aldehyde capable of forming a methylol or a substituted methylolgroup and having not more than 8 carbon atoms is satisfactory, so longas it does not possess some other functional group or structure whichwill conflict with the resinification reaction or with the subsequentoxyalkylation of the resin, but the use of formaldehyde, in its cheapestform of an aqueous solution, for the production of the resins isparticularly advantageous. Solid polymers of formaldehyde are moreexpensive and higher aldehydes are both less reactive, and are moreexpensive. Furthermore, the higher aldehydes may undergo other reactionswhich are not desirable, thus introducing difficulties into theresinification step. Thus acetaldehyde, for example, may undergo analdol condensation, and it and most of the higher aldehydes enter intoself-resinification when treated with strong acids or alkalis. On theother hand, higher aldehydes frequently beneficially affect thesolubility and fusibility of a resin. This is illustrated, for example,by the difierent characteris- "cs of the resin prepared frompara-tertiary amylphenol and formaldehyde on one hand and a comparableproduct prepared from the same phenolic reactant and heptaldehyde on theother hand. The former, as shown in certain subsequent examples, is ahard, brittle solid, whereas the latter is soft and tacky, and obviouslyeasier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. Theemployment of furfural requires careful control for the reason that inaddition to its aldehydic function, furfural can form vinylcondensations by virtue of its unsaturated structure. The production ofresins from furfural for use in preparing products for the present 8process is most conveniently conducted with weak alkaline catalysts andoften with alkali metal carbonates. Useful aldehydes, in addition toformaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde,2-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and benzaldehyde,furfural and glyoxal. It would appear that the use of glyoxal should beavoided due to the fact that it is tetrafunctional. However, ourexperience has been that, in resin manufacture and particularly asdescribed herein, apparently only one of the aldehydic functions entersinto the resinification reaction. The inability of the other aldehydicfunction to enter into the reaction ispresumably due to sterichindrance. Needless to say, one can use a mixture of two or morealdehydes although usually this has no advantage.

Resins of the kind which are used as intermediates for the compoundsused in the practice of this invention are obtained with the use of acidcatalysts or alkaline catalysts, or without the use of any catalyst atall. Among the useful alkaline catalysts are ammonia, amines, andquaternary ammonium bases. It is generally accepted that when ammoniaand amines are employed as catalysts they enter into the condensationreaction and, in fact, may operate by initial combination with thealdehydic reactant. The compound hexam'ethylenetetramine illustratessuch a combination. In light of these various reactions it becomesdifficult to present any formula which would depict the structure of thevarious resins prior to oxyalkylation. More will be said subsequently asto the difference between the use of an alkaline catalyst and an acidcatalyst; even in the use of an alkaline catalyst there is considerableevidence to indicate that the products are not identical where difierentbasic materials are employed. The basic materials employed include notonly those previously enumerated but also the hydroxides of the alkalimetals, hydroxides of the alkaline earth metals, salts of strong basesand weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: paraand ortho-cresol;paraand orthoethyl-phenol; 3-methyl-4-ethyl-phenol;3-methyll-propyl-phenol; 2-ethyl-3-methyl-phenol; 2- propyl 3 methylphenol; paraand orthopropyl phenol; para tertiary butyl phenol;para-secondary butyl phenol; para tertiaryamyl phenol; para secondaryamyl phenol; para tertiary hexyl phenol; para isooctylphenol; orthophen'yl phenol; para phenylphenol; thymol; ortho benzyl phenol;parabenzyl-phenol; para cyclohexyl phenol; paratertiary decyl phenol;para dodecyl phenol; para-tetradecylphenol; para-octadecyl-phenol;para-nonyl-phenol; para-menthyl-phenol; paraeicosanyl-phenol;para-docosanyl-phenol; paratetracosanyl-phenol; para betanaphthyl-phenol; para-alpha-naphthyl-phenol; para-pentadecyl-phenol;that of the formula C3H1 oH3 oH2)itH-om C3H1 C 3Hapara-tertiary-alkyl-phenols of the formula cs n cetyl-phenols;,para-cumyl-phenol; phenols of the formula R1-C-R2 in which R1represents a straight chain hydrocarbon radical containing at least 7carbon atoms and R2 and R3 represent hydrocarbon radicals the totalnumber of carbon atoms attached to the tertiary carbon being at least11; and phenols of the formula Be in in which R1 represents an alkylhydrocarbon radical containing at least 7 carbon atoms in a straightchain and R2 represents an alkyl hydrocarbon radical containing at least2 carbon atoms, the total number of carbon atoms in R1 and R2 being atleast 11; and the corresponding orthopara substituted meta-cresols and3,5-xylenols.

For convenience, the phenol has previously been referred to asmonocyclic in order to differentiate from fused nucleus polycyclicphenols, such as substituted naphthols. Specifically, monocyclic islimited to the nucleus in which the hydroxyl radical is attached.Broadly speaking, where a substituent is cyclic, particularly aryl,obviously in the usual sense such phenol is actually polycyclic althoughthe phenolic hydroxyl is not attached to a fused polycyclic nucleus.Stated another way, phenols in which the hydroxyl groupis directlyattached to a condensed or fused polycyclic structure, are excluded.This matter, however, is clarified by the following consideration. Thephenols herein contemplated for reactionmay be indicated by thefollowing formula:

in which R is selected fromthe class consisting of hydrogen atoms andhydrocarbon radicals having not more than 24 carbon atoms, with theproviso that one occurrence of R is the hydrocarbon substituent and theother two occurrences are hydrogen atoms, and with the further provisionthat one,or=both of the 3 and positions may be methyl substituted.

The above formula possibly can be restated more conveniently in the=f0llowing manner, to wit, that the phenol employed is of the followingformula, with the proviso that R is a hydrocarbon substituent located inthe 2,4,6 position, again with the provision as to 3 or 3,5 methylsubstitution. This is conventionalnomenclature, numbering the variouspositions in the usual clockwise manner, beginning with the hydroxylposition as one:

The manufacture of thermoplastic phenolaldehyde resins, particularlyfrom formaldehyde and a difunctional phenol, i. e., a phenol in whichone of the three reactive positions (2,4,6) has been substituted by ahydrocarbon group, is well known. As has been previously pointed out,there is no objection to a methyl radical provided it is present in the3 or 5 position.

Thermoplastic or fusible phenol-aldehyde resins are usually manufacturedfor the varnish trade and oil solubility is of prime importance. Forthis reason, common reactants employed are butylated phenols, amylatedphenols, phenylphenols, etc. The methods employed in manufacturing suchresins are similar to those employed in the manufacture of ordinaryphenolformaldehyde resins, in that either an acid or alkaline catalystis usually employed. The procedure frequently differs from that employedin the manufacture of ordinary phenol-aldehyde resins in that phenol,being water-soluble, reacts readily with an aqueous aldehyde solutionwithout further difficulty, while when a waterinsoluble phenol isemployed some modification is usually adopted to increase theinterfacial surface and thus cause reaction to take place. A commonsolvent is sometimes employed. Another procedure employs rather severeagitation to create a large interfacial area. Once the reaction startsto a moderate degree, it is possible that both reactants are somewhatsoluble in the partially reacted mass and assist in hastening thereaction. We have found it desirable to employ a small proportion of anorganic sulfoacid as a catalyst, either alone or along with a mineralacid like sulfuric or hydrochloric acid. For example, alkylated aromaticsulfonic acids are effectively employed. Since commercial forms of suchacids are commonly their alkali salts, it is sometimes convenient to usea small quantity of such alkali salt plus a small quantity of strongmineral acid, as shown in the examples below. If desired, such organicsulfoacids may be prepared in situ in the phenol employed, by reactingconcentrated sulfuric acid with a small proportion of the phenol. Insuch cases Where xylene is used as a solvent and concentrated sulfuricacid is employed, some sulfonation of the Xylene probabl occurs toproduce the s-ulfo-acid. Addition of a solvent such as Xylene isadvantageous as hereinafter described in detail. Another variation ofprocedure is to employ such organic sulfo-acids, in the form of theirsalts, in connection with an alkali-catalyzed resinification procedure.Detailed examples are included subsequently.

Another advantage in-the manufacture of the thermoplastic or fusibletype of resin by the acid catalytic procedure is that, since adifuctional phenol is employed, on excess of an aldehyde, for instanceformaldehyde, may be employed without too marked a change in conditionsof reaction and ultimate product. There is usually little. if any,advantage, however, in using an excess over and above the stoichiometricproportions for the reason that such excess maybe lost and wasted. 'Forall practical purposes the molar ratio of formaldehyde to phenol ma belimited to 0.9 to 1.2, with 1.05 as the preferred ratio, or sufficient,at least theoretically, to convert the remaining reactive hydrogen atomof each terminal phenolic nucleus. Sometimes when higher aldehydes areused an excess of aldehydic reactant can be distilled 01f and thusrecovered from the reaction mass. This same procedure may be used withformaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularlyformaldehyde, may be increased over the simple stoichiometric ratio ofone-to-one or thereabouts. With the use of alkaline catalyst it has beenrecognized that considerably increased amounts of formaldehyde may used,as much as two moles of formaldehyde, for example, per mole of phenol,or even more, with the result that only a small part of such aldehyderemains uncombined or is subsequently liberated during resinification.Structures which have been advanced to explain such increased use ofaldehydes are the following:

on on -omo-O-orno-om-O Such structures may lead to the production ofcyclic polymers instead of linear polymers. For this reason, it has beenpreviously pointed out that, although linear polymers have by far themost important significance, the present invention dies not excluderesins of such cyclic structures.

Sometimes conventional resinification procedure is employed using eitheracid or alkaline catalysts to produce low-stage resins. Such resins maybe employed as such, or may be altered or converted into high-stageresins, or in any event, into resins of higher molecular weight, byheating along with the employment of vacuum so as to split oif water orformaldehyde, or both. Generally speaking, temperatures employed,particularly with vacuum, ma be in the neighborhood of 175 to 250 C., orthereabouts.

It may be Well to point out, however, that the amount of formaldehydeused may and does usually affect the length of the resin chain.Increasing the amount of the aldehyde, such as formaldehyde, usuallyincreases the size or molecular weight of the polymer.

In the hereto appended claims there is specified, among other things,the resin polymer containing at least 3 phenolic nuclei. Such minimummoleclar size is most conveniently determined as a rule by cryoscopicmethod using benzene, or some other suitable solvent, for instance, oneof those mentioned elsewhere herein as a solvent for such resins. As amatter of fact, using the procedures herein described or anyconventional resinification procedure will yield products usually havingdefinitely in excess of 3 nuclei. In other words, a resin having anaverage of 4, 5 or 5 /2 nuclei per unit is apt to be formed as a minimumin resinification, except under certain special conditions wheredimerization may occur.

However, if resins are prepared at substantially higher temperatures,substituting cymene, tetralin, etc., or some other suitable solventwhich boils or refluxes at a higher temperature, instead of xylene, insubsequent examples, and if one doubles or triples the amount ofcatalyst, doubles or triples the time of refluxing, uses a marked excessof formaldehyde or other aldehyde, then the average size of the resin isapt to be distinctly over the above values, for example, it may average7 to 15 units. Sometimes the expression lowstage resin or low-stageintermediate is employed to mean a stage having 6 or 7 units or evenless. In the appended claims we have used lowstage to mean 3 to 7 unitsbased on average molecular weight.

The molecular weight determinations, of course, require that the productbe completely soluble in the particular solvent selected as, forinstance, benzene. The molecular weight determination of such solutionmay involve either the freezing point as in the cryoscopic method, or,less conveniently perhaps, the boiling point in an ebullioscopic method.The advantage of the ebullioscopic method is that, in comparison withthe cryposcopic method, it is more apt to insure complete solubility.One such common method to employ is that of Menzies and Wright (see J.Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method fordetermining molecular Weights will serve, although almost any procedureadopted has inherent limitations. A good method for determining themolecular weights of resins, especially solvent-soluble resins. is thecryoscopic procedure of Krumbhaar which employs diphenylamine as asolvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co.1947) Subsequent examples will illustrate the use of an acid catalyst,an alkaline catalyst, and no catalyst. As far as resin manufacture perse is concerned, we prefer to use an acid catalyst, and particularly amixture of an organic sulfo-acid and a mineral acid, along with asuitable solvent, such as xylene, as hereinafter illustrated in detail.However, we have obtained products from resins obtained by use of analkaline catalyst which were just as satisfactory as those obtainedemploying acid catalysts. Sometimes a combination of both types ofcatalysts is used in different stages of resinification. Resins soobtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., thosereferred to as high-stage resins, are conveniently obtained bysubjecting lower molecular weight resins to vacuum distillation andheating. Although such procedure sometimes removes only a modest amountor even perhaps no low polymer, yet it is almost certain to producefurther polymerization. For instance, acid catalyzed resins obtained inthe usual manner and having a molecular weight indicating the presenceof approximately 4 phenolic units or thereabouts may be subjected tosuch treatment, with the result that one obtains a resin havingapproximately double this molecular weight. The usual procedure is touse a secondary step, heating the resin in the presence or absence of aninert gas, including steam, or by use of vacuum.

We have found that under the usual conditions of resinificationemploying phenols of the kind here described, there is little or notendency to form binuclear compounds, i. e., dimers, resulting from thecombination, for example, of 2 moles of a phenol and one mole offormaldehyde, particularly Where the substituent has not more than 11*i-or carbon atoms. bonatoms in a substituent approximates '7 or 8,there may besome tendency to dimerization. The. usualprocedure to obtaina dimer involves an enormously large excess of the phenol, for instance,8 to moles per mole of aldehyde.

Where the hydrocarbon substituent contains 9 carbon atoms or more thereis an increased tendency to form a measurable amount of dimers.

The cogeneric formation of a relatively small amountof dimers isunimportant and there is no reasonto separate the dimers prior tooxyalkylation and use.. Among the phenomena observed as the hydrocarbonsubstituent increases in sizearethe following:

(1) There is a tendency to form dimers even though molar equivalents oran excess of an aldehyde is used.. This is probably related to one ormoreof. the following: (a) decreased reactiveness or sluggishness due tothe increased'size of the reactant; (b) statistically lessopportunityfor reaction because the point of reaction, the reactive hydrogen atom,is diluted through greater molecular area or space; (0) the structure assuch may afford decreased opportunity for reaction.

(2) There is an increased tolerance towards trifunctional phenols.Indeed,v trifunctional phenols having a metasubstituent of theapproximate size. of those now referred to, i. e., 9 carbonatoms or morefrequently produce soluble phenol-aldehyde resins when treated in. themanner. herein described. For example, cardanol or hydrogenated cardanolgive soluble, fusible resins, the solubility and fusibility beingrelated to the size of the substituent.

(3)1 Increasing the size, of the side cha n increases thecarbon-oxygenratiov of the finished resin and ultimatel causes greater solubility inhydrocarbon solvents,,particularly SOIVel'lt-S'Of low polarity.

Where the hydrocarbon substituent has 3 carbon atoms or less there islittle tendency to form dimers,.but certain differences in behaviour ascompared with phenols having higher hydrocarbon. substituents becomesignificant and noticeable. Thus, there is a decreased tolerance towardtrifunctional phenols, the phenols become more highly reactive, thecarbon-oxygen ratio of the finished resin becomes less, ultimately.causing decreased solubilit in hydrocarbon solvents, and

the-tendency to form resins which harden, cure, or crosslink, eventhough the phenol be difunctional, increases. For this reason it isoften advantageous to use higher aldehydes, rather than formaldehyde,where the phenol used as a 2,4,6 substituent .of 3 carbon atoms or less.Substituted dihydroxy-diphenylmethanes obtained from substituted phenolsare not resins as that term is used herein, but the presence of somedimer in a resin'does not preclude its use.

One need not use a single phenolic reactant, as mixtures of. phenolicreactants give resins which are well adapted for the preparation ofproducts used in the. practice of the invention, and, in many'cases,products obtained from mixtures of different phenolic reactants haveadvantages, either from the standpoint of production cost ordemulsification effectiveness. Thus, the cresols, theethyl phenols andthe propyl phenols (difunctional in all cases) are obtainable at acostof 50-to 60% of the cost of some of the other common difunctionalphenols, such as butyl, amyl, octyl and nonyl phenols. A mixture of.phenols giving a product ofsubstantially the same effectiveness as thatobtained from the more expensive Where the number ofJcarphenol. afiordsva. definite economic advantage. Further, sometimes mixtures of phenolsgive products which appear to be more effective than productsobtainedlfrom a single phenol. Thus, products obtained from mixtures ofbutyl or amyl phenol, methyl phenol, nonyl phenol, decyl phenol andother phenols in some instances appear to have. a greater, effectivenessthan products obtained from single phenols, even though there is not anysaving in cost in the production of products from such mixtures.

Because of low cost, mixtures in which cresol is oneof the phenolicreactants areof particular importance. We have used mixtures employing acresol and another phenol in molar ratios ranging from 1:9 to -9:1,.andfound them effective. Di.- functional' xylenols, although they giveeffective agents in mixtures of this kind, are usually more expensiveand do. not ofier this economic advantage.

Although any conventional procedure ordinarily. employed may be used inthe manufacture of the herein contemplated resins or, for that matter,such resins may be purchased in the open market, we have found itparticularly desirable to use the procedures describedelsewhere herein,and employing a combination of an organic sulfoacid and a mineral acidas a catalyst, and xylene as a solvent. By way of illustration, certainsubsequent examples are included, butit is to be understood the hereindescribed invention is not concerned with the resins per se or with anyparticular method of manufacture but is con.- cerned with the use ofderivatives obtained by the subsequent oxyalkylation thereof. Thephenol-aldehyde-resins may be prepared in any suitable manner.

O xyalkylation, particularly 0 x y e th y1 a ti on which is thepreferred reaction, depends on contact between a non-gaseous phase and agaseous phase. It can, for example, be carried out by melting thethermoplastic resin and subiecting it to treatmentwith ethylene oxide orthe like, or by treating a suitable solution or suspension. Since themelting points of the resins are often higher than desired in theinitial stage of oxyethylation, we have found it advantageous to use asolution or suspension of thermoplastic resin in an inert solvent suchas xylene. Under such circumstances, the resin obtained in the usualmanner is dissolved by heating in xylene under a reflux condenser or inany other suitable manner. Since xylene or an equivalent inert solventis present or may be present during oxyalkylation, it is obvious thereis no objection to having a solvent present during the resinifying stageif, in addition to being inert towards the resin, it is also inerttowards the reactants and also inert towards water. Numerous solvents,particularly of aromatic or cyclic nature, are suitably adapted for suchuse. Examples of such solvents are xylene, cymene, ethyl benzene, propylbenzene, mesitylene, decalin (decahydronaphthalene), tetralin(tetrahydronaphthalene), ethylene glycol diethylether, diethylene glycoldiethylether, and tetraethylene glycol dimethylether, or mixtures of oneor more. Solvents such as dichloroethylether, or dichloropropylether maybe em-- ployed either alone or in mixture but have the objection thatthe chlorine atom in the compound may slowly combine with the alkalinecatalyst employed in oxyethylation. Suitable solvents may be selectedfrom this group for molecular weight determinations.

The use of such solvents is a convenient expedient in the manufacture ofthe thermoplastic resins, particularly since the solvent gives a moreliquid reaction mass and thus prevents overheating, and also because thesolvent can be employed in connection with a reflux condenser and awater trap to assist in the removal of water of reaction and also waterpresent as part of the formaldehyde reactant when an aqueous solution offormaldehyde is used. Such aqueous solution, of course, with th ordinaryproduct of commerce containing about 37 /2% to 40% formaldehyde, is thepreferred reactant. When such solvent is used it is advantageously addedat the beginning of the resinification procedure or before the reactionhas proceeded very far.

The solvent can be removed afterwards by distillation with or withoutthe use of vacuum, and a final higher temperature can be employed tocomplete reaction if desired. In many instances it is most desirable topermit part of the solvent, particularly when it is inexpensive, e. g.,xylene, to remain behind in a predetermined amount so as to have a resinwhich can be handled more conveniently in the oxyalkylation stage. If amore expensive solvent, such as decalin, is employed, xylene or otherinexpensive solvent may be added after the removal of decalin, ifdesired,

In preparing resins from difunctional phenols it is common to employreactants oftechnical grade. Th substituted phenols herein contemplatedare usually derived from hydroxybenzene. As a rule, such substitutedphenols are. comparatively free from unsubstituted phenol. We havegenerally found that the amount present is considerably less than 1% andnot infrequently in the neighborhood of Tsth of 1%, or even less. Theamount of the usual trifunctional phenol, such as hydroxybenzene ormetacresol, which can be tolerated is determined by the fact that actualcross-linking, if it takes place even infrequently, must not besufficient to cause insolubility at the completion of the resinificationstage or the lack of hydrophile properties at the completion of theoxyalkylation stage.

The exclusion of such trifunctional phenols as hydroxybenzene ormetacresol is not based on the fact that the mere random or occasionalinclusion of an unsubstituted phenyl nucleus in the resin molecule or inone of several molecules, for example, markedly alters thecharacteristics of the oxyalkylated derivative. The presence of a phenylradical having a reactive hydrogen atom available or having ahydroxymethyl or a substituted hydroxymethyl group present is apotential source of cross-linking either during resinification oroxyalkylation. Cross-linking leads either to insoluble resins or tonon-hydrophilic products resulting from the oxyalkylation procedure.With this rationale understood, it is obvious that trifunctional phenolsare tolerable only in a minor proportion and should not be present tothe extent that insolubility is produced in the resins, or that theproduct resulting from oxyalkylation is gelatinous, rubbery, or at leastnot hydrophile. As to the rationale of resinification, note particularlywhat is said hereafter in differentiating between resoles, Novolaks, andresins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organicsolvent-soluble resins are usually linear but may be cyclic. Such morecomplicated structure may be formed, particularly if a resin prepared inthe usual manner is converted into a higher stage resin by heattreatment in vacuum as previously mentioned. This 14 again is a reasonfor avoiding any opportunity for cross-linking due to the presence ofany appreciable amount of trifunctional phenol. In other words, thepresence of such reactant may cause cross-linking in a conventionalresinification procedure, or in the oxyalkylation procedure,

or in the heat and vacuum treatment if it is employed as part of resinmanufacture.

Our routine procedure in examining a phenol for suitability forpreparing products to be used in practicing the invention is to preparea resin employing formaldehyde in excess (1.2 moles of formaldehyde permole of phenol) and using an acid catalyst in the manner describedhereinafter in Example 1a. If the resin so obtained is solvent-solublein any one of the aromatic or other solvents previously referred to, itis then subjected to oxyethylation. During oxyethylation a temperatureis employed of approximately 150 to 165 C. with addition of at least 2and advantageously up to 5 moles of ethylene oxide per phenolichydroxyl. The oxyethylation is advantageously conducted so as to requirefrom a few minutes up to 5 to hours. If the prodnot so obtained issolvent-soluble and self-dispersing or emulsifiable, or has emulsifyingproperties, the phenol is perfectly satisfactory from th standpoint oftrifunctional phenol content. The solvent may be removed prior to thedispersibility or emulsifiability test. When a product becomes rubberyduring oxyalkylation due to the presence of a small amount oftrireactive phenol, as previously mentioned, or for some other reason,it may become extremely insoluble, and no longer qualifies as beinghydrophile as herein specified. Increasing the size of the aldehydicnucleus, for instance using heptaldehyde instead of formaldehyde,increases toleranc for trifunctional phenol.

The presence of a trifunctional or tetrafunctional phenol (such asresorcinol or bisphenol A) is apt to produce detectable cross-linkingand insolubilization but will not necessarily do so, especially if theproportion is small. Resinifica- 5 tion involving difunctional phenolsonly may also produce insolubilization, although this seems to be ananomaly or a contradiction of what is sometimes said in regard toresinification reactions involving difunctional phenols only. This so ispresumably due to cross-linking. This appears to be contradictory towhat one might expect in light of the theory of functionality inresinification. It is true that under ordinary circumstances, or ratherunder the circumstances of conventional resin manufacture, theprocedures employing difunctional phenols are very apt to, and almostinvariably do, yield solvent-soluble, fusible resins. However, whenconventional procedures are employed in connection with resins so forvarnish manufacture or the like, there is involved the matter of color,solubility in oil, etc.

When resins of the same type are manufactured for the hereincontemplated purpose, i. e., as a raw material to be subjected tooxyalkylation, no such criteria of selection are no longer pertinent.

Stated another way, one may use more drastic conditions ofresinification than those ordinarily employed to produce resins for thepresent purposes. Such more drastic conditions of resini- 70 ficationmay include increased amounts of catalyst, higher temperatures, longertime of reaction, subsequent reaction involving heat alone or incombination with vacuum, etc. Therefore, one is not only concerned withthe resinification 7t reactions which yield the bulk of ordinary resinsfrom difunctional' phenols but also and particularly with the minorreactions of ordinary resin manufacture which are of importance in thepresent invention for the reason that they occur under more drasticconditions of resinincation which may be employed advantageously attimes, and they may lead to cross-linking.

In this connection it may be well to point out that part of thesereactions are now understood or explainable to a greater or lesserdegree in light of a most recent investigation. Reference is made to theresearches of Zinke and his 00-- workers, I-Iultzsch and his associates,and to von Eulen and his co-workers, and others. As to a bibliography ofsuch investigations, see Carswell, Phenoplasts, chapter 2. Theseinvestigators limited much of their work to reactions involv-- ingphenols having two or less reactive hydrogen atoms. Much of what appearsin these most recent and most upto-date investigations is pertinent tothe present invention insofar that much of it is referring toresinification involving difunctional phenols.

For the moment, it may be simpler to consider a most typical type offusible resin and forget for the time that such resin, at least undercertain circumstances, is susceptible to further complications.Subsequently in the text it will be pointed out that cross linking orreaction with excess formaldehyde may take place even with one of suchmost typical type resins. This point is made for the reason thatinsolubles must be avoided in order to obtain the products hereincontemplated for use as demulsifying agents.

The typical type of fusible resin obtained from a para-blocked orortho-blocked phenol is clearly differentiated from the Novolak type orresole type of resin. Unlike the resole type, such typical typepara-blocked or orthoblocked phenol resin may be heated indefinitelywithout passing into an infusible stage, and in this respect is similarto a Novolak. Unlike the Novolak type the addition of a furtherreactant, for instance, more aldehyde, does not ordinarily alterfusibility of the difunctional phenol-aldehyde type resin; but suchaddition to a Novolak causes cross-linking by virtue. of the availablethird functional position.

What has been said immediately preceding is Subject to modification inthis respect: It is well known, for example, that difunctional phenols,for instance, paratertiaryainylphenol, and an aldehyde, particularlyformaldehyde, may yield heat-hardenable resins, at least under certainconditions, as for example the use of two moles of formaldehyde to oneof phenol, along with an alkaline catalyst. This peculiar hardening orcuring or cross-linking of resins obtained from difunctional phenols hasbeen recognized by various authorities.

The compounds herein used must be hydrophile or sub-surface-active orsurface-active as hereinafter described, and this precludes theformation of insolubles during resin manufacture or the subsequent stageof resin manufacture where heat alone, or heat and vacuum, are employed,or in the oxyalkylation procedure. In its simplest presentation therationale of resinification involving formaldehyde, for example, and adifunctional phenol would not be expected to form cross-links. However,cross-linking sometimes occurs and it may reach the objectionable stage.However, provided that the preparation of resins simply takes intocognizance the present knowledge of the subject, and employingpreliminary, exploratory routine examinations as herein indicated, thereis not the slightest difficulty in preparing a very large number ofresins of various types and from various reactants, and by means ofdifferent catalysts by different procedures, all of which are eminentlysuitable for the herein described purpose.

Now returning to the thought that crosslinking can take place, even whendifunctional phenols are used exclusively, attention is directed to thefollowing: Somewhere during the course of resin manufacture there may bea potential cross-linking combination formed but actual cross-linkingmay not take place until the subsequent stage is reached, 1. e., heatand vacuum stage, or oxyalkylation stage. This situation may be relatedor explained in terms of a theory of flaws, or Lockerstellen, which isemployed in explaining flaw-forming groups due to the fact that a CHzOHradical and H atom may not lie in the same plane in the manufacture ofordinary phenol-aldehyde resins.

Secondly, the formation or absence of forma tion of insolubles may berelated to the aldehyde used and the ratio of aldehyde, particularlyformaldehyde, insofar that a slight variation may, under circumstancesnot understandable, produce insolubilization. The formation of theinsoluble resin is apparently very sensitive to the quantity offormaldehyde employed and a slight increase in the proportion offormaldehyde may lead to the formation of insoluble gel lumps. The causeof insoluble resin formation is not clear, and nothing is known as tothe structure of these resins.

All that has been said previously herein as regards resinification hasavoided the specific ref erence to activity of a methylene hydrogenatom. Actually there is a possibility that under some drastic conditionscross-linking may take place through formaldehyde addition to themethylene bridge, or some other reaction involving a methylene hydrogenatom.

Finally, there is some evidence that, although the meta positions arenot ordinarily reactive, possibly at times methylol groups or the likeare formed at the meta positions; and if this were the case it may be asuitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instanceformaldehyde, is not to be taken as a criterion of rejection for use asa reactant. In other Words, a phenol-aldehyde resin which isthermoplastic and solvent-soluble, particularly if xylene-soluble, isperfectly satisfactory even though retreatment with more aldehyde maychange its characteristics markedly in regard to both fusibility andsolubility. Stated another Way, as far as resins obtained fromdifunctional phenols are concerned, they may be eitherformaldehye-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is tobe noted that they are thermoplastic phenol-aldehyde resins derived fromdifunctional phenols and are clearly distinguished from Novolaks Orresoles. When these resins are produced from difunctional phenols andsome of the higher aliphatic aldehydes, such as acetaldehyde, theresultant is often a comparatively soft or pitchlike resin at ordinarytemperature. Such resins become comparatively fluid at to C. as a ruleand thus can be readily oxyalkylated, preferably oxyethylated, withoutthe use of a solvent.

Reference has been made to the use of the Word "fusiblef Ordinarily athermoplastic resin is identified as one which can be heated repeatedlyand still not lose its thermoplasticity. It is recognized, however, thatone may have a resin which is initially thermoplastic but on repeatedheating may become insoluble in an organic solvent, or at least nolonger thermoplastic, due to the fact that certain changes take placevery slowly. As far as the present invention is concerned, it is obviousthat a resin to be suitable need only be sufficiently fusible to permitprocessing to produce our oxyalkylated products and not yield insolublesor cause insolubilization or gel formation, or rubberiness, aspreviously described. Thus resins which are, strictly speaking, fusiblebut not necessarily thermoplastic in the most rigid sense that suchterminology would be applied to the mechanical properties of a resin,are useful intermediates. The bulk of all fusible resins of the kindherein described are thermoplastic.

The fusible or thermoplastic resins, or solventsoluble resins, hereinemployed as reactants, are water-insoluble, or have no appreciablehydrophile properties. The hydrophile property is introduced byoxyalkylation. In the hereto appended claims and elsewhere theexpression waterinsoluble is used to point out this characteristic ofthe resins used.

In the manufacture of compounds herein employed, particularly fordemulsification, it is obvious that the resins can be obtained by one ofa number of procedures. In the first place, suitable resins are marketedby a number of companies and can be purchased in the open market; in thesecond place, there are a wealth of examples of suitable resinsdescribed in the literature. The third procedure is to follow thedirections of the present application.

The following examples, 1a to 15a, give specific directions forpreparing oxyalkylation-susceptible, Water-insoluble, organicsolvent-soluble, fusible, phenolic resins which may be used to preparethe products used in the practice of the invention. Additionally, wedirect attention to Examples 1a to 188a of our application Serial No.8,722, filed on the same day this application Was filed, as illustratingsuitable resins for this purpose. Examples lb to 9b illustrate carryingout the oxyalkylation procedure to produce products useful in thepractice of the invention. Again we direct attention to Examples lb to16b, 24b and 25b of our application Serial No. 8722 as illustratngproducts useful for the practice of this invention. Examples 10 to 30illustrate the use of the products for demulsification.

Monoalkyl (Clo-C20, principally 012-014) benzene monosulfonic acidsodium salt" Xylene (Examples of alkylaryl sulfonic acids which serve ascatalysts and as emulsifiers particularly in the form of sodium saltsinclude the following:

SOsH

ill

18 His an alkyl hydrocarbon radical having 12-14 carbon atoms.

R is an alkyl radical having 3-12 carbon atoms and n represents thenumeral 3, 2, or 1, usually 2, in such instances Where R contains lessthan 8 carbon atoms.

With respect to alkylaryl sulfonic acids or the sodium salts, we haveemployed a monoalkylated benzene monosulfonic acid or the sodium saltthereof wherein the alkyl group contains 10 to 14 carbon atoms. We havefound equally effective and interchangeable the following specificsulfonic acids or their sodium salts: A mixture of diand tripropylatednaphthalene monosulfonic acid; diamylated naphthalene monosulfonic acid;and nonyl naphthalene monosulfonic acid.

The equipment used was a conventional twopiece laboratory resin pot. Thecover part of the equipment had four openings: One for reflux condenser;one for the stirring device; one for a separatory funnel or other meansof adding reactants; and a thermometer well. In the manipulationemployed, the separatory funnel insert for adding reactants was notused. The device was equipped with a combination reflux and Watertrapapparatus so that the single piece of apparatus could be used as eithera reflux condenser or a water trap, depending on the position of thethree-way glass stopcock. This permitted convenient Withdrawal of waterfrom the water trap. The equipment, furthermore, permitted any settingof the valve without disconnecting the equipment. The resin pot washeated with a glass fiber electrical heater constructed to fit snuglyaround the resin pot. Such heaters, with regulators, are readilyavailable.

The phenol, formaldehyde, acid catalyst, and solvent were combined inthe resin pot above described. This particular phenol was in the form ofa flaked solid. Heat was applied with gentle stirring and thetemperature was raised to -85" C., at which point a mild exothermicreaction took place. This reaction raised the temperature toapproximately l05-l10 C. The reaction mixture was then permitted toreflux at -105 C. for between one and one and one-half hours. The refluxtrap arrangement was then changed from the reflux position to the normalwater entrapment position. The water of solution and the water ofreaction were permitted to distill out and collect in the trap. As thewater distilled out, the temperature gradually increased toapproximately C. which required between 1.5 to 2 hours. At this pointthe Water recovered in the trap, after making allowance for a smallamount of water held up in the solvent, corresponded to the expectedquantity.

The solvent solution so obtained was used as such in subsequentoxyalkylation steps. We have also removed the solvent by conventionalmeans, such as evaporation, distillation or vacuum distillation, and wecustomarily take a small sample of the solvent solution and evaporatethe solvent to note the characteristics of the solvent-free resin. Theresin obtained in the operation above described was clear, light ambercolored, hard, brittle, and had a melting point of -165 C.

Attention is directed to the fact that tertiary butylphenol, in presenceof a strong mineral acid 75 as a catalyst and using formaldehyde,sometimes .meal rather than dry flakes.

' yieldsa resinwhich apparently .has.azvery slight amount ofcross-linkage. Such resin issimilar to the one described. above exceptthat it is somewhat opaque, and its melting point is higher than the onedescribed above and there is a tendency to cure. Such a resin is.generally dispersible in xylene but not soluble 'to give a clearsolution. Such dispersion can beoxyalk'ylatedin the same manner as theclear resin. If desired, a minor proportion of another and inertsolvent, such as diethyleneglycol diethylether, may be employed alongwithxylene, to give a clear solution prior to oxyalkylation. This factof 'solubilization shows vthe present resin molecules are still quitesmall, as

. contrasted with the very large size of extensively cross-linked resinmolecules. If following a given procedure with a given lot of thephenol, such a resin is obtained, the amount of catalyst employed isadvantageously reduced slightly or the time of reflux reduced slightly,or'both, or an acid.

such as oxalic acid is used instead of hydrochloric acid. Purely asa-matter of convenience due to better solubility in xylene, we prefer touse a clear resin but if desired either type may be employed.

Example 2a.

The same procedure was followed as in Example 101. preceding, and thematerials used the same,

except that the para-tertiary butyl-phenol was replaced by anequalamount of para-secondary butyl-phenol. The phenol was a solid of asomewhat mushyappearance, resembling moist corn- The appearance of theresin was substantially identical with that described in Example 1a,preceding. The solventfree resin was reddish-amber in color, somewhatopaque but completely xylene-soluble. It was semi-soft or pliable inconsistency. See what is said in Example 101., preceding, in regard tothe opaque appearance of the resin. What is said there applies withequal forceand efiect in the instant example.

Example 30.

Grams Para-tertiary amylphenol (1.0 mole) 164 Formaldehyde 37% (1.0mole) l- 81 I-ICl (concentrated) 1.5

Monoalkyl (Clo-C20, principally 012-014) benzene monosulfonic acidsodium salt 0.8 Xylene 100 The procedure followed was the same as thatused in Example la, preceding. The-phenol employed was a flaked solid.The solvent-free resin was dark red in color, hard, brittle, with amelting point of 128-140 C. It was xylene-soluble.

Example 4a The same procedure was employed as inExample 1a, preceding,using-198 grams of com mercial styrylphenol and .150 grams of xylene.Styrylphenol is atwhite solid. The resinwas reddish black in color, hardand brittle with amelting point of about 80 to 85 C.

The same procedure was followedas in Exam- .There-Was :a modestprecipitate of an insoluble "material, approximately 15 grams,

Furfural ,which .had an insoluble sponge-like carbona- .ceousappearance. :It .was removed :byflltration of the xylenesolution:as:in.Example.12a preceding.- The resulting-.solvent-freeres'inwasclear, reddish-amber. in color, soft to fluid .in consist-.ency, and xylene-soluble.

Xylene The phenohacid catalyst and 50. grams of the xylene were combinedin'the resinpotxpreviously described underiExamplela. The initialmixture'did not includethealdehyde. The mixture was heated-with stirringto I approximately 150 C. and permitted to reflux.

'The remainderofthe xylene, 50 gramsywas then mixed'with theacetaldehyde; and this mixture was .added slowly to the materials in theresin pot, with constant stirring, :by means of the separatory funnelarrangement previously mentioned in thedescription of the resin pot inExample 1a. Approximately 30 minutes were required to add this amount ofdiluted aldehyde. A mildexothermic reaction'waslnoted. at the firstaddition of the aldehyde. The temperature slowly dropped,as water. of.reaction'formed, to about 100 to C withithe reflux temperaturebeingdetermined by the boilingipoint of water. After all the aldehyde hadbeen. added, the reactants were-permitted torefluxfor 'between an hourto an hour and a half before removingthe water Example 7 a.

Grams Para-tertiary amylphenol 164 96 Potassium carbonate 8"The'furfural was shakenwith dry sodium car- "bonateprior to use,--toeliminate anyacids, etc. The procedure employed was substantially thatdescribed in 'detail in Technical'Bulletin No. 109 of the QuakerOats'Company, Chicago, Illinois. The above reactants were heated underthe reflux condenser for'two hours in the same resin pot arrangementdescribed in Example 1a. The separatory funnel device was not employed.No xylene or othersolvent'was' added. The amount of materialvaporizedand. condensedwas comparatively small except forzthe-water of reaction.At the end of this heating or refluxperiod, the trap was set to removethe water. The'maximum temperature during and after removal of Water wasapproximately 202 C. The material in the trap represented 16cc.water-and 1.5 cc. furfural. "The resinwa's a bright black, hard resin,xylene-soluble, and had a melting point of to C., with some tendencytowards being slowly curable. We have also successfully followed thissame procedure using 3.2 grams of potassium carbonate instead of 8.0grams.

Monoalkyl (Clo-C20, principally 012-014) benzene monosulfonic acidsodium salt 2.0 Xylene 200 The above reactants were combined in a resinpct similar to that previously described, equipped with stirrer andreflux condenser. The reactants were heated with stirring under refluxfor 2 hours at 100 to 110 C. The resinous mixture was then permitted tocool sufficiently to permit the addition of 15 ml. of glacial aceticacid in 150 cc. H2O. On standing, a separation was efiected, and theaqueous lower layer drawn off. The upper resinous solution was thenwashed with 300 ml. of water to remove any excess HCI-IO, sodiumacetate, or acetic acid. The xylene was then removed from the resinoussolution by distilling under vacuum to 150 C. The resulting resin wasclear, light amber in color, and semifiuid or tacky in consistency.

Example 9a This resin was obtained by the vacuum distillation of resinof Example 3a. Vacuum distillation was conducted up to 250 C. at 25 mm.Hg. The resulting resin was hard, brittle, amber colored, and had aslightly higher melting point than the resin prior to vacuumdistillation, to wit 140-145 C. It was xylene soluble. The molecularweight, determined cryoscopically using benzene, was approximately 1400.

Example 10a Grams Commercial para-tertiary amylphenol 164 Formaldehyde81 Monoalkyl (Cm-C20, principally 012-014) benzene monosulfonic acidsodium salt .6 Xylene 200 No catalyst was added in this example. Thereactants were placed in an autoclave and stirred while heating to atemperature of approximately 160 C. The total period of reaction was 5hrs. During the early part of this period the temperature was 156 C.with a gauge pressure of 110 pounds. During the last part of the period,probably due to the absorption of formaldehyde, the pressure dropped to'75 pounds gauge pressure while the temperature held at about 150 C.After this 5 hour reaction period the autoclave was allowed to cool. Theliquids were withdrawn and the xylene solution of the resin was decantedaway from the small aqueous layer. The xylene solution, containing a bitof the aqueous layer carried over mechanically, was subjected to vacuumdistillation up to 150 C. at 25 mm. Hg.

The resulting resin was fairly hard and brittle, xylene-soluble, dark,amber in color, with a melting point of 55 to 66 C., and a molecularweight of 490. If desired, one may use considerably higher pressure 50as to speed up the reaction and also in order to obtain resins of highermolecular weight. We have employed the same procedure with moderatelyhigher temperatures and definitely higher pressures.

Example 11a Grams Menthylphenol, technically pure (1.0 mole) 2-32Acetaldehyde (1.0 mole) 44: Concentrated H2804 2 Xylene 100 22 Thephenol, acid catalyst,'and 50 grams of the xylene were combined in theresin pot previously described under Example la. The initial mixture didnot include the aldehyde. The mixture was 5 heated with stirring toapproximately 150 C. and

permitted to reflux.

The remainder of the xylene, 50 grams, was then mixed with theacetaldehyde; and this mixture was added slowly to the materials in theresin pot, with constant stirring, by means of the separatory funnelarrangement previously mentioned in the description of the resin pot inExample 1a. Approximately 30 minutes were required to add this amount ofdiluted aldehyde. A mild exothermic reaction was noted at the firstaddition of the aldehyde. The temperature slow- 1y dropped, as water ofreaction formed, to about 100 to 110 C., with the reflux temperaturebeing determined by the boiling point of water. After all the aldehydehad been added, the reactants were permitted to reflux for between anhour to an hour and a half before removing the water by means of thetrap arrangement. After the water was removed the remainder of theprocedure was essentially the same as in Example 1a. The solvent-freeresin was hard but not brittle, reddish amber in color and had a meltingpoint of about 50 to 55 C.

Example 12a Grams Nonylphenol (22.5 moles) 4,980 Formaldehyde (37%, 25.5moles) 2,076

Monoalkyl (Cm-C20, principally 012-014) benzene monosulfonic acid sodiumsalt 15 NaOH (in 200 cc. H2O) 67 Xylene 4,000

The above reactants were combined in a 5- gallon autoclave and heatedwith stirring, under pressure. The reactants were heated for 1% hoursafter temperature had reached 1 0 C. The maximum temperature was 190 C.and the maximum pressure was 245 pounds per square inch.

After cooling, more than sufflcient (148 grams) glacial acetic acid wasadded to neutralize the alkaline catalyst. The resin mixture wasdiluted, washed and distilled. The resulting solvent-free resin, aftervacuum (25 mm.) distillation to 150 C., was semi-hard to pliable, ambercolored, and xylene-soluble. If the vacuum distillation is furthercarried to 200 C., the resulting product is a hard, brittle resin with amelting point of 90 to 95 C. It is amber in color and xylene-soluble.

Example 13a Grams Elcosanyl phenol purity as described) (1.0 mole) 41660 Formaldehyde (37%) (1.1 mole) 9 Concentrated I-ICl 3 Monoalkyl(Cw-C20, principally ClZ-Chl) benzene monosulfonic acid sodium salt 1.5Xylene 23 what tacky feel, possibly the :result ofithe. impuritiesinathe .phenol used.

Ewample 14a.

The procedure was the same as that of Example 13a except that the 416grams of eicosanyl phenol werereplaced by 44'? grams of docosanylphenol, prepared in the same way but with theuse of ethyl laurateinstead of ethyl caprate. The resin obtained was similar in appearanceto that of Example 13a but was somewhat softer.

Example 15a The procedure followed was the same as that of Example 13a.except the eicosanyl phenol was replaced by 478 grams of tetracosanylphenol, prepared in the same manner but with the use of ethyl myristate.The resin obtained was similar in appearance to that of Example 13a butwas considerably softer.

Phenols with hydrocarbon substituents containing to 24 carbon atoms havealso been prepared in other ways, for example, by the monochlorinationof waxes from Pennsylvania crudes having molecular weights indicatingthe presence of 20 to 24 carbon atoms in the molecule. A- phenolprepared in this way, using zinc chloride as the alkylation catalyst,converted to a resin as in Example 13a by using 447 grams of the phenolto allow for the presence of impurities, gave a dark, tacky to semi-hardresin. The out was selected to have an average molecular weight of 22carbon atoms, to give a mixture of difunctional phenols with 20 to 24carbon atom substituents, although the presence of lighter or heaviermaterials in the selected fraction, which presumably carried over intothe phenol, is not improbable, because a product having an averagemolecular weight of, say, 22 carbon atoms, is equivalent to eithera020-6324 fraction or a C1s-C2s fraction, etc.

In a number of the foregoing examples, phenols have been identifiedwithoutspecific designation of the position of substitution or thestructure of the substituent radical. In such cases, the phenols meantare either the commercial products distributed under these names, or, ifthe products are not commercially available, the products obtained bycustomary syntheses from phenol, meta-cresol' or 3,5-xylenol, andconsist mainly of the para-substituted product, usually associated withsome of the ortho-substituted product, perhaps a very small proportionof metasubstituted material, some impurities, etc. Also, it is to beunderstood that all of the products of the foregoing examples, unless itis otherwise stated in the example, are soluble in xylene, at least toan. extent suflicient to permit the use of xylene as the solvent inoxyalkylation.

As far as the manufacture of resins is concerned it is usually mostconvenient to employ a catalyst such as illustrated by previousexamples.

It is extremely difiicult to depict the structure of a resin derivedfroma single phenol. When mixtures of phenols are used, even in equimolarproportions, the structure of the resin is even more indeterminable. Inother words, a mixture involving para-butylphenol and para-amylphenolmight have an alternation of the two nuclei or one might have a seriesof butylated:

nuclei and then a series of amylated nuclei. If a mixture of aldehydesis employed, for instance, acetaldehyde and butyraldehyde, oracetaldehyde and formaldehyde, or ben'zaldchyde and acetaldehyde, thefinal structure of the resin;

Liv

becomes even morelcompli'cated and possibly tiepends-on the relativereactivity of the aldehydes. For that matter, one might "be producing.simultaneously two different. resins, in what would actually be. a.mechanical .mixture, although such mixture'might exhibit someuniqueproperties as compared withcacmixture of the'same two resins preparedseparately... Similarly, as has been sug gested, one might use acombination of oxyalkylating agents; for instance; one mightpartially-oxyalkylate with ethylene oxide and then finishoff withpropylene oxide. It is understood that the use oioxyalkylatedderivatives of such resins, derived from such plurality of reactantsinstead of being limited to a single reactant from each of the threeclasses, is contemplated and here included for the reason that they areobvious variants-- Havingobtained a suitable resin of the kinddescribed, such resin is subjected to treatment with a lowmolal reactivealpha-beta olefin oxide so as to render theproduct distinctly hydrophilein nature as indicated by the-fact that it becomes self-emulsifiable ormiscible or soluble in water, or self-dispersible, or has emulsifyingproperties. The olefin oxides employed are characterized by thefact-that they contain not over 4 carbon atoms: and areselected from theclass consisting of ethylenev oxide, propylene oxide, butyleneoxide,glycide, and methyl-glycide. Glycide may as, of course, consideredas a hydroxy propylene oxide and methyl glycide as a hydroxy butyleneoxide. In any event, however, all such reactants contain the reactiveethylene oxidering and may be best consideredas derivatives of orsubstituted ethylene oxides. The solubilizing eiiect of the oxide isdirectly proportional to the percentage of oxygen present, orspecifically, to the oxygencarbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it "is263; and in methyl giycide, 1:2. In such compounds, the ratio is veryfavorable to the'production' of hydrophile or surfaceactive-properties.However, the ratio, in propylone oxide, is 1:3, and in butylene oxide,1:4. Obviously; such latter two reactants are satisfactorily employedonly where theresin composition is such as to make incorporation of thedesired property practicaL In other cases, they may produce marginallysatisfactory derivatives, or even unsatisfactory derivatives. They areusable in conjunction with the three more favorable alkylene oxides inall cases. For instance, after one or several propylene oxide orbutylene oxide molecules have been attached to the resin molecule,oxyalkylation may be satisfactorily continued using the more'favorablemembers of the class, to produce the desired hydrophile product. Usedalone, these two reagents may in some cases fail to produce sufficientlyhydrophile derivatives because of their relatively low oxygen-carbonratios.

Thus, ethylene 'oxideis much more efiective than propylene oxide, andpropylene oxide is more effective than butylene oxide. Hydroxy propyleneoxide (glycide) is more effective than propylene oxide. Similarly,hydroxy butylene oxide (methyl glycide) is more efiective than butyleneoxide. Since ethylene oxide is the cheapest alkylene oxide available andis reactive, its use is definitely advantageous, and especially inzlightof its high oxygencontent. Propylene oxide is less reactive thanethylene oxide, and butylene oxide is definitely less reactive thanpropylene oxide. On the other hand, glycide may react with almostexplosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the products used inthe practice of the present invention are prepared is advantageouslycatalyzed by the presence of an alkali. Useful alkaline catalystsinclude soaps, sodium acetate, sodium hydroxide, sodium methylate,caustic potash, etc. The amount of alkaline catalyst usually is between0.2% to 2%. The temperature employed may vary from room temperature toas high as 200 C. The reaction may be conducted with or Withoutpressure, 1. e., from zero pressure to approximately 200 or even 300pounds gauge pressure (pounds per square inch). In a general way, themethod employed is substantially the same procedure as used foroxyalkylation of other organic materials having reactive phenolicgroups.

It may be necessary to allow for the acidity of a resin in determiningthe amount of alkaline catalyst to be added in oxyalkylation. Forinstance, if a nonvolatile strong acid such as sulfuric acid is used tocatalyze the resinification reaction, presumably after being convertedinto a sulfonic acid, it may be necessary and is usually advantageous toadd an amount of alkali equal stoichiometrically to such acidity, andinclude added alkali over and above this amount as the alkalinecatalyst.

It is advantageous to conduct the oxyethylation in presence of an inertsolvent such as xylene, cymene, decalin, ethylene glycol diethylether,diethyleneglycol diethylether, or the like, although with many resins,the oxyalkylation proceeds satisfactorily without a solvent. Sincexylene is cheap and may be permitted to be present in the final productused as a demulsifier, it is our preference to use xylene. This isparticularly true in the manufacture of products from low-stage resins,i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated,the pressure readings of course represent total pressure, that is, thecom-- bined pressure due to xylene and also due to ethylene oxide orwhatever other oxyalkylating agent is used. Under such circumstances itmay be necessary at times to use substantial pressures to obtaineffective results, for instance, pressures up to 300 pounds along withcorrespondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such asxylene can be eliminated in either one of two ways: After theintroduction of approximately 2 or 3 moles of ethylene oxide, forexample, per phenolic nucleus, there is a definite drop in the hardnessand melting point oi the resin. At this stage, if xylene or a similarsolvent has been added, it can be eliminated by distillation (vacuumdistillation if desired) and the subsequent intermediate, beingcomparatively soft and solvent-free, can be reacted further in the usualmanner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with suchsolvent present and then eliminate the solvent by distillation in thecustomary manner.

Another suitable procedure is to use propylene oxide or butylene oxideas a solvent as well as a reactant in the earlier stages along withethylene oxide, for instance, by dissolving the powdered resin inpropylene oxide even though oxyalkylation is taking place to a greateror lesser degree.

After a solution has been obtained which represents the original resindissolved in propylene oxide or butylene oxide, or a mixture whichincludes the oxyalkylated product, ethylene oxide is added to react withthe liquid mass until hydrophile properties are obtained. Since ethyleneoxide is more reactive than propylene oxide or butylene oxide, the finalproduct may contain some unreacted propylene oxide or butylene oxidewhich can be eliminated by volatilization or distillation in anysuitable manner.

Attention is directed to the fact that the resins herein described mustbe fusible or soluble in an organic solvent. Fusible resins invariablyare soluble in one or more organic solvents such as those mentionedelsewhere herein. It is to be emphasized, however, that the organicsolvent employed to indicate or assure that the resin meets thisrequirement need not be the one used in oxyalkylation. Indeed solventswhich are susceptible to oxyalkylation are included in this group oforganic solvents. Examples of such solvents are alcohols andalcohol-ethers. However, where a resin is soluble in an organic solvent,there are usually available other organic solvents which are notsusceptible to oxyalkylation, useful for the oxyalkylation step. In anyevent, the organic solvent-soluble resin can be finely powdered, forinstance to 100 to 200 mesh, and a slurry or suspension prepared inxylene or the like, and subjected to oxyalkylation. The fact that theresin is soluble in an organic solvent or the fact that it is fusiblemeans that it consists of separate molecules. Phenol-aldehyde resins ofthe type herein specified possess reactive hydroxyl groups and areoxyalkylation susceptible.

Considerable of what is said immediately hereinaiter is concerned withthe ability to vary the hydrophile properties of the compounds used inthe process from minimum hydrophile properties to maximum hydrophileproperties. Even more remarkable, and equally diiiicult to explain, arethe versatility and utility of these compounds as one goes from minimumhydrophile property to ultimate maximum hydrophile property. Forinstance, minimum hydrophile property may be described roughly as thepoint where two ethyleneoxy radicals or moderately in excess thereof areintroduced per phenolic hydroxyl. Such minimum hydrophile property orsub-surfaceactivity or minimum surface-activity means that the productshows at least emulsifying properties or self-dispersion in cold or evenin warm distilled water (15 to 40 C.) in concentrations of 0.5% to 5.0%.Thees materials are generally more soluble in cold water than warmwater, and may even be very insoluble in boiling water. Moderately hightemperatures aid in reducing the viscosity of the solute underexamination. Sometimes if one continues to shake a hot solution, eventhough cloudy or containing an insoluble phase, one finds that solutiontakes place to give a homogeneous phase as the mixture cools. Suchself-dispersion tests are conducted in the absence of an insolublesolvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2moles of ethylel'ie oxide per phenolic nucleus or the equivalent) butinsufiicient to give a sol as described immediately preceding, then, andin that event hydrophile properties are indicated by the fact that onecan produce an emulsion by having present 10% to 50% of an inert solventsuch as xylene. All that one need to do is to have a xylene solutionwithin the range of 50m parts by weight 27 of oxyalkylatedderivativesand 50 to parts by weight of xylene and mix such solution 'with'one, two'or three times its volume of distilled water ands'hake vigorously so asto obtain an emulsion which 'may be of the oil-in-water type or thewater-in-oil type (usually the former) but, in any-event, is due to thehydrophile-hydrophobe balance of the oxyalkylated derivative. We :prefer"simply to use the xylene diluted derivatives, which are describedelsewhere, for this test rather than evaporate the solvent and employany more ela'boratetests, if the solubility is not sufficient to permitthe simple sol test in water previously noted.

If the product is not readily Water soluble'it may be dissolved in ethylor methyl alcohol, ethylene "glycol diethyleth-er, or diethylene glycol'diethyl- .ether, with a little acetone added if "required, making arather concentrated solution, for instance 40% to50%, and thenadding-enough of the concentrated alcoholic'or equivalent'solution 'togive the previously suggested 0.5% -to 5.0% strength solution. If *theproduct is self-dispersing ('i. e., if the oxyalkylated product is aliquid or a liquid solution 'selfemulsifiable ,such sol or dispersion isreferred to "as-at least *sern'istable in the sense that sols,emulsions, 'or dispersions prepared are relatively-stable, if theyremain at least "for some period of time, for instance 30'minutes to twohours, before showing any markedseparation. Suchtests'are conducted atroom temperature (22 C.). Needless to say, .a test can be .made inpresence of an insoluble solvent such as 5% to of 'xylene,-as noted inprevious examples. If such mixture, i. e.,-containing 'a waterinsolublesolvent, isat'leastsemistable, obviously the solvent-free product-wouldbe ,even more so. Surface-activity representing .an advanced'hydrophile-hydroph'obe balance can also be determined by the use ofconventional measurements hereinafter described. One outstandingcharacteristic property indicating surface-activity in a'material 'isthe ability to form a permanent foam in dilute aqueous solution, forexample, less than 0.5%, when in the higher oxyalkylated stage, and toform an emulsion in the lower and intermediate stages of oxyalkylation.

Allowance 'must be made :for the presence -'of .a solvent in the finalproduct in relation to the r hydrophile properties of the final product.The principle involved in the manufactureof 'the herein contemplatedcompounds foruse-as demulsify- 'ing agents, is based on the conversionof a'hydro- .phobe or non-hydrophile compound'or mixture of compounds.into products which are distinctly hydrophile, at least to the extentthat they have emulsifying properties or are self-emulsifying; that .is,when shaken with "water they produce stable or semi-stable suspensions,or, in the presence of a water-insoluble solvent, such as "xylene, anemulsion. In demulsification, it is sometimes preferable to use aproduct having markedly enhanced hydrophile properties overand above theinitial stage .of self-emulsifiability, although we have found that withproducts of the type used herein, most eflicacious results are obtainedwith products'w'hich do not have hydrophile properties beyond the stageof self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols whichshow typical properties comparable to ordinary surface-active agents.Such conventional surface-activity may be measured by determining thesurface tension and the 'interfacial tension against parafiin oil 'orthe like. At the initia'land lov/er stages of oxyalkylation,surface-activit is not suitably determined in this same manner but onemay employ an 'emulsification test. Emulsions come into existence as arule throughthe presence of a surfaceactive emulsifying agent. 'Somesurface-active emulsifying agents such as mahogany soap may produce awater-in-oii emulsion or an cit-inwater emulsion depending upon theratio of the two phases, "degree of agitation, concentration ofemulsifying agent, etc.

The same is true in regard to the oxyalkylated res-ins herein specified,particularly in the lower stage of oxya'lkylation, these-calledsub-surface active stage. The surfa'ct-ac'tive propeties are readilydemonstrated by producing a xylene-water emulsion. A suitable procedureis as follows: The oxyalkylated resin is dissolved in an equal weight ofxylene. Such 5050 solution is then mixed with 1-3 volumes of water andshaken to produce an emulsion. The amount of xylene is invariablysuificient to reduce even a tacky resinous product to a solution whichis readily dispersible. 'The emulsions so produced areusuallyxylene-in-Water emulsions (oil in-water type) particularly whenthe amount of distilled water used is at least slightly in excess of thevolume ofxylene solution and also if shaken vigorously.

At times, particularly in the lowest stage of oxyalkylation, one mayobtain a :water-in-xylene emulsion (water-in-oil type) which is apt toreverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained frompara-tertiarybutylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst and then followed .by oxyalkylationusing 2 moles of ethylene oxide for each phenolic hydroxyl, is help ful.Such resin prior to oxyalkylation has a molecular weight indicatingabout l units per resin molecule. Such resin, when diluted with an equalweight of xylene, will serve to illustrate the above emulsificationtest.

In a few instances, the resin may not be sufficiently soluble in xylenealone but may require the addition of some ethylene glycol diethyletheras described elsewhere. It is understood that suchmixture, or any othersimilar mixture, is considered the equivalent of xylene for the purposeof this test.

In many cases, there is no doubt as to the presence or absence ofhydrophile or surfaceactive characteristics in the products used inaccordance with this invention. They dissolve or disperse in water; andsuch dispersions foam readily. With borderline cases, i. e., those whichshow only incipient hydrophile or surface-active property(sub-surface-activity) tests for emulsifying properties orself-dispersibility are useful. The fact that a reagent is capable ofproducing a dispersion in water is proof that it is distinctlyhydrophile. In doubtful cases, comparison can be made with thebutylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxidehave been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may maskthe point at which a solvent-free product on mere dilution in a testtube exhibits self-emulsification. For this reason, if it is desirableto determine the approximate point where self-emulsification begins,then it is better to eliminate the xylene or equivalent from a smallportion of the reaction mixture and test such portion. In some cases.such xylene-free resultant may show initial or incipient hydrophileproperties, whereas in presence of xylene such properties would not benoted. In other cases, the first objective indication of hydrophileproperties may be the capacity of the material to emulsify an insolublesolvent such as xylene. It is to be emphasized that hydrophileproperties herein referred to are such as those exhibited by incipientself-emulsification or the presence of emulsifying properties and gothrough the range of homogeneous dispersibility or admixture with watereven in presence of added water-insoluble solvent and minor proportionsof common electrolyt-es as occur in oil field brines- Elsewhere, it ispointed out that an emulsification test may be used to determine rangesof surface-activity and that such emulsification tests employ a xylenesolution. Stated another way, it is really immaterial whether a xylenesolution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation ofrange of hydrophile properties, and also in light of what has been saidas to the variation in the eifectiveness of various alkylene oxides, andmost particularly 4 of all ethylene oxide, to introduce hydrophilecharacter, it becomes obvious that there is a wide variation in theamount of alkylene oxide employed, as long as it is at least 2 moles perphenolic nucleus, for producing products useful for the practice of thisinvention. Another variation is the molecular size of the resin chainresulting from reaction between the difunctional phenol and the aldehydesuch as formaldehyde. It is well known that the size and nature orstructure of the resin polymer obtained varies somewhat with theconditions of reaction, the proportions of reactants, the nature of thecatalyst, etc. I

Based on molecular weight determinations, most of the resins prepared asherein described, particularly in the absence of a secondary heatingstep, contain 3 to 6 or 7 phenolic nuclei with approximately 4 or nucleias an average. More drastic conditions of resinification yield resins ofgreater chain length. Such more intensive resinification is aconventional procedure and may be employed if desired. Molecular weight,of course, is measured by any suitable procedure, particularly bycryoscopic methods; but using the same reactants and using more drasticconditions of resinification one usually finds that hi her molecularweights are indicated by higher melting points of the resins and atendency to decreased solubility. See what has been said elsewhereherein in regard to a secondary step involving the heating of a resinwith or without the use of vacuum.

We have previously pointed out that either an alkaline or acid catalystis advantageously used in preparing the resin. A combination ofcatalysts is sometimes used in two stages; for instance, an alkalinecatalyst is sometimes employed in a first stage, followed byneutralization and addition of a small amount of acid catalyst in asecond stage. It is generally believed that even in the presence of analkaline catalyst, the number of moles of aldehyde, such asformaldehyde, must be greater than the moles of phenol employed in orderto introduce methylol groups in the intermediate stage. There is noindication that such groups appear in the final resin if prepared by theuse of an acid catalyst. It is possible that such groups may appear inthe finished resins prepared solely with an alkaline catalyst; but wehave never been able to confirm this fact in an examination of a largenumber of resins prepared by ourselves. Our preference, however, is touse an acid-catalyzed resin, particularly employing aformaldehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have beenable todetermine, such resins are free from methylol groups. As a matterof fact, it is probable that in acid-catalyzed resinifications, themethylol structure may appear only momentarily at the very beginning ofthe reaction and in all probability is converted at once into a morecomplex structure during the intermediate stage.

One procedure which can be employed in the use of a new resin to prepareproducts for use in the process of the invention is to determine thehydroxyl value by the Verley-Biilsing method or its equivalent. Theresin as such, or in the form of a solution as described, is thentreated with ethylene oxide in presence of 0.5% to 2% of sodiummethylate as a catalyst in step-wise fashion. The conditions ofreaction, as far as time or per cent are concerned, are within the rangepreviously indicated. With suitable agitation the ethylene oxide, ifadded in molecular proportion, combines within a comparatively shorttime, for instance a few minutes to 2 to 6 hours, but in some instancerequires as much as 8 to 24 hours. A useful temperature range is from125 to 225 C. The completion of the reaction of each addition ofethylene oxide in step-wise fashion is usually indicated by thereduction or elimination of pressure. An amount conveniently used foreach addition is generally equivalent to a mole or two moles of ethyleneoxide per hydroxyl radical. When the amount of ethylene oxide added isequivalent to approximately 50% by weight of the original resin, asample is tested for incipient hydrophile properties by simply shakingup in Water as is, or after the elimination of the solvent if a solventis present. The amount of ethylene oxide used to obtain a usefuldemulsifying agent as a rule varies from 70% by weight of the originalresin to as much as five or six times the weight of the original resin.In the case of a resin derived from para-tertiary butylphenol, as littleas 50% by weight of ethylene oxide may give suitable solubility. Withpropylene oxide, even a greater molecular proportion is required andsometimes a resultant of only limited hydrophile properties isobtainable. The same is true to even a greater extent with butyleneoxide. The hydroxylated alkylene oxides are more effective insolubilizing properties than the comparable compounds in which nohydroxyl is present.

Attention is directed to the fact that in the subsequent examplesreference is made to the stepwise addition of the alkylene oxide, suchas ethylene oxide. It is understood, of course, there is no objection tothe continuous addition of alkylene oxide until the desired stage ofreaction is reached. In fact, there may be less of a hazard involved andit is often advantageous to add the alkylene oxide slowly in acontinuous stream and in such amount as to avoid exceeding the higherpressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced fromdifunctional phenols and some of the higher aliphatic aldehydes, such asacetaldehyde, the resultant is a comparatively soft or pitch-like resinat ordinary temperatures. Such resins become comparatively fluid at 31':to 165 C;asarulazandthus can be readily oxyalkylated, preferablyoxyethylated, without the use of a solvent.

What has beensaid previously is not intended to suggest that anyexperimentation is necessary to. determine the degree of oxyalkylation,and particularly oxyethylation. What has been said previously issubmitted primarily to emphasize the fact that these; remarkableoxyalkylated resins having surface activity-show unusual properties asthe hydrophile-character varies from a minimum to an ultimatemaximum.One should not-underestimate the utility of any of these prod nets in asurface-active or sub-surface-active range without testing themffordemulsification. A few simple laboratory tests which can be-conducted inaroutine manner will usually giveall the information that is required.

For instance; asimple rule.- to'follow is to-prepare a resin having atleast three phenolic nuclei and being organic: solvent-solub1e.Oxyethylate such resin, usingthe following four ratios of .rnoles ofethylene oxide per 'phenolicunit equivalent: 2- to 1; Sto- 1; 10to-1;and-15 to-l. From a sample:

of each pro'duct'rernove-any solvent-that may be present, such asxylene. 5.0% solutions-in distilled'water, as previously indicated. Amere examination of such series will.

generally reveal an approximate range of minimum hydrophile'character,moderate hydrophile" character, and maximum: hydrophile character. Ifthe. 2 to 1 ratio does notshow minimum hydrophile characterby-test of ithe solventefree prode not, then one should test its capacity to forman.

emulsion when admixedwith xylene or other insoluble solvent;

using. 2 /2 to 4 moles per phenolic nucleus will serve.- Moderatehydrophile character should befor instance. 5% of.xy1ene,'yields aproduct which.

will. give, at least temporarily, a transparent or translucent sol ofthe kind just described. The formation of a permanentfoam, when a 0.5%to 5.0% aqueous solution is shaken, is an excellenttest for surfaceactivity. Previous reference has been made to the fact that otheroxyalkylating agents may require the use of increased amounts of.alkylene oxide. However, if one does not even care to go to the troubleof calculating molecular weights, one-can simply arbitrarily preparecompounds containing ethylene oxide equivalent to about 50% to 75% byweight, for example 65% by weight, .of the resin to be oxyethylated; asecond example using approximately 200% to 300% by weight, and a thirdexample using about 500% to 750% by weight, to explore the range ofhydrophile hydrophobe balance.

A practical examination of the factor of oxy-- alkylation level can bemade by a very simple test using a pilot plant autoclave having acapacity of about to gallons as herein-after described. Suchlaboratory-prepared rout ne compounds can then be tested for solubilityand, generally speaking, this is all that isreouired to give'a suitablevariety covering the hydrophile-" Prepare 0.5% and If neither test showsthe re-- quired minimum hydrophileproperty, repetition hydrophobe range.Allthese tests, as stated, are- ,make certain "determinations in orderto maize the quickest'approach to the appropriate oxyalkylation range.Forinstance, one should know (a) the molecularv size, indicating thenumber of phenolic units; (12) the nature of the aldehydic residue,which:is usually CH2; and (c) the nature of thehydrocarbon substituent.With such information one is in substantially the'same'position as ifone had-personally made the resin prior to oxyethylation.

For instance, the molecular weight of the in ternal structural units ofthe-resin of the following over-simplified i formula:

R I .R a

(12:1 to 13,"or even more) isr given approximately. by. the formula:(mol. wt. of phenol -2). plus mol. wt..of methylene orsubstituted'methylene. radical. weight oftheiresinwouldbe. n timesthevalue for. theinternalunit .plusthe values for the terminal .units.The leftehand .terminal unit. of. the above structural. formula, .it.will be. seen, isidene tical with the recurringiriternal.unit exceptthatv it hasone extra hydrogen. The-right-handter minalunit lackslthemethylene bridge-element. Using oneinternal unit .of a resin as thebasic. element, a. resins molecular weight is given ap.-

proximately bytaking (11.. plus 2). times the Weight of the internalelement. Where the resin mole-.

cule has only 3 phenolic nuclei as in the structure shown, thiscalculation will be in .error by several per cent;.but as it. growslarger, to contain 6, 9, or. 12phenolic nuclei, the formula comes to bemore than satisfactory. Using such an approximate weight one need onlyintroduce, for example, twomolal weights of.ethylene oxide or slightlymore,.per phenolic nucleus, to produce a,

product of minimal hydrophile character, Further oxyalkylation givesenhanced hydrophile character. Although we have prepared and testedalarge number of oxyethylated products of the type described herein, wehave found no instance where the. use of less than 2 moles of ethyleneoxide per phenolic nucleus gave desirable products.

The following examples, lo to 9b, are included to exemplify theproduction of suitable oxyalkylated products from resins, specifically,resins described in a number of'the foregoing Examples la to 15a. givingexact and complete details for the carrying out of the procedure. Wedirect attention to Examples 1a to 188a and Examples 1b to 16b and 24band 25b of our application Serial No. 8,722 as illustrating the samematters.

Example 1b The resin employed in'the acid-catalyzed paratertiarybutylphenol formaldehyde resin of Example 1a.. (suchxresin canxbepurchased in the The. molecular open market.) The resin is powdered andmixed with an equal weight of xylene so as to obtain solution by meansof a stirring device employing a reflux condenser. 170 grams of theresin are dissolved in or mixed with 170 grams of xylene. To the mixturethere is added 1.7 grams of sodium methylate powder. The solution orsuspension is placed in an autoclave and approximatel 400 grams ofethylene oxide by weight are added in 6 portions of approximately 65 to75 grams each. After each portion is added, the reaction is permitted totake place for approximately 4 hours. The temperature employed isapproximately 150 to 165 C. and a maximum gauge pressure ofapproximately 150 pounds per square inch. The minimum gauge pressure isapproximately 20 pounds per square inch. At the end of each 4- hourperiod there is no further drop in pressure, thus indicating that allthe ethylene oxide present has reacted and the pressure registered onthe gauge represents the vapor pressure of xylene at the indicatedtemperature. After the sixth and final portion of ethylene oxide hasbeen added, a test is made on the resultant.

In one such operation, the resultant, when cold, was a viscous opaqueliquid, emulsifiable in water even in presence of the added xylene. Thisindicated that incipient emulsification in absence of xylene probablyappeared at the completion of the fourth addition of ethylene oxide. Inother words, 150 grams or 175 grams of ethylene oxide are sufficient togive incipient hydrophile properties in absence of xylene. The initialpoint approximates ethylene oxide equal to slightly less than 100% ofthe weight of the initial resin. In this instance in order to obtaingreater solubility, the amount of ethylene oxide used for reaction wasincreased by a second series of additions using substantially the sameconditions of reaction as noted previously. Such series was continueduntil, as an upper limit, 500 grams of ethylene oxide had beenintroduced on the basis of the original 170 grams of resin. See theattached table for data as to the compound in which the ratio ofethylene oxide to resin is about 2:1. A compound of this constitution,containing a small amount of xylene, was light amber in color, misciblewith water and had a viscosity resembling that of castor oil.

Example 2b The same reactants, and procedure was employed as in Examplepreceding, except that propylene oxide was employed instead of ethyleneoxide. The resultant, even on the addition of the alkylene oxide in theweight proportions of the previous example, has diminished hydrophileproperties in comparison with the resultants of Example lb. Thisillustrates the point that propylene oxide and butylene oxide give:products of lower levels of hydrophile properties than does ethyleneoxide.

Ewample 3b The same reactants and procedure were followed as in Example1b, except that one mole of glycide was employed initially per hydroxylradi-'- cal. This particular reaction was conducted with extreme careand the glycide was added in small amounts representing fractions of amole. Ethylene oxide was then added, following the procedure of Examplelb, to produce products of greater hydrophile properties. We areextremely hesitant to suggest even the experimental use of glycide andmethylglycide for the reason that 34 disastrous results may be obtainedeven in experimentation with laboratory quantities.

Example 4b The same procedure is followed as in Example lb except thatinstead of employing the resin employed in Example 1b, there wassubstituted instead an equal weight of resin of Example 2a. The productsobtained were similar in appearance, color and viscosity to those ofExample 1b.

Example 5b Example 6b The same reactants and procedure were employed asin Example 15, except that the acidcatalyzed styrylphenolformaldehyderesin of Example 4a was used instead of the butyl'phenol resin. Theoxyethylated products are similar in appearance, color, solubility,etc., to the products of Example 11).

Example 7b The resin employed was the acid-catalyzed resin fromeicosanyl phenol described in Example 13a. The procedure followed wasthat of Example lb, 310 grams of resin solution containing 45% xylenebeing used with the addition of 3.5 grams of sodium methylate. The datain tabular form are as follows:

. Remarks as to Batch EtO Time Max. Max. lres- No. Added Required Temp.sure ggggg ig Grams Hours C. #/sq. in. l 4 163 Insoluble. 2 65 4 160 150Do. 3 55 4 158 150 Emulsifiable. 4. 75 4 150 D0. 5 65 4 155 150 D0. 6 754 163 150 D0.

Example 85 The resin employed was the docosanyl phenol of Example 14a.310 grams of resin solution containing 45% xylene were used, with theaddition of 3.5 grams of sodium methylate. The procedure of Example lbwas followed. The data in tabular form are as follows:

The resin used was the tetracosanyl phenol of Example 15a. 310 grams ofresin solution containing 45% xylene were used with the addition of 3.5grams of sodium methylate. The procedure a5 followed was that of:Example 1b. .Thedatain tabular form are as follows:

The resins, prior to oxyalkylation, vary from tacky, viscous liquids tohard, high-melting solids. Their color varies from a light yellowthrough amber, to a deep red or even almost black. 'In the manufactureor" resins, particularly hard resins, as the reaction progresses thereaction mass frequently goes through a liquid state to a sub resinousor semi-resinous state,-often characterized by being tacky or sticky, toa final complete resin. As the resin is subjected to oxyalkyl ationthese same physical changes tendto take place in reverse. If one startswith a solid resin, oxyalkylation tends to make 'ititacky orsemiresinous and further oxyalkylation makes the tackiness disappear andchanges the product to a liquid. Thus, as the resin is oxyalkylatedit'decreases in viscosity, that is, becomes more liquid or changes froma solid to aliquid, particularly when it is converted to thewater-dispersible or water-soluble stage. The color of theoxyalkylatedderivative is usually considerably lighter than the original productfrom which it is made, varying from a pale straw color to an amber orreddish amber. The viscosity usually varies from that of an oil, likecastor oil, to that of a thick viscous sirup. Some products are waxy.The presence of a solvent, such as 15% Xylene or the like thins theviscosity considerably'and also reduces the color in dilution. No unduesignificance need be attached to the color for the reasonlthat if thesame compound is prepared in glass and in iron, the latter usually hassomewhatdarker color. If the resins areprepared as customarily employedin varnish resin manufacture, i. e., a procedure that excludes thepresence of oxygen during the resinification and subsequent cooling ofthe resin, then of course the initial resin is much lighter in color. Wehave employed some resins which initially are almost water-white andalso yield alighter colored final product.

The same procedure as described above has been applied to a largevariety of resins of the kind described previously, including resinsobtained from mixtures of phenols, and we have found that theseoxyalkylated products having the required minimum hydrophile properties,are all efifective for use in the process of the invention. In. manycases resins used were obtained from ald'ehydes other than formaldehyde,i. e., higher aldehydes having not over 8 carbon atoms. Similarly, someof the resins instead of being ob-- tained by use of acid catalysts wereobtained by use of alkaline catalysts or sequential use of both types ofcatalyst. Insome instances the resins were obtained by a process whichinvolved a secondary step of heating alone or under vacuum.

In our application Serial No. 8,722 there is a table which illustratesthe efiect of oxyalkylation of a wide range of phenolic resins, andshows that many 'efiective compounds for demulsification purposesrequire but about one-half this amount of alkylene oxide compound, inparticular ethylene oxide,'for example, from 150% to 200% by weight..Of.the products illustrated inthe table insaid application serial'No.8,722, those derived :from products illustrated by Examples 1a to .188aof thatapplication are usefulior the practice of the present inventionand illustrate it. Largeramounts of ethylene oxide,.for example, amountsup to six times the weight of the initial resin may be used, even thoughthe solubility of such products may. in some cases be. less thanthesolubility of derivatives obtained with lesseramounts of alkyleneoxide.

The oxyethylated products, in the presence of the solvent, were liquidsvarying in viscosity from relative mobility to a viscosity approachingthat of ,castor oil orlightly blown vegetable oils. They I I varied incolor from straw colored or light amber to very dark brownish'or reddishcolored. Itis to be understood that when these products are used fordemulsification, it is unnecessary to separate them from the solventused in their preparation, and ordinarily commercial products will, ifprepared" with the use of a solvent, be. distributed without removal ofthe solvent, andirequently with the addition of other solvent materials,other agents, etc.

The following examples, Examples lc-3c, are

included toillustrate the technique of testing the effectiveness of thedemulsifiersagainst oil field emulsions. It is to be understood thatintheindustrial use of these products theyare used in accordance withstandard practices, some of which are-subsequently described. I

The demulsifier employed-was the oxyalkylate'd derivative of the resinof Example 2a prepared from para-secondary butylphenol and formaldehydeusing an acid catalyst oXyethylated-with an amountof ethyleneoxide equalin weight to the Weightof theresin, following the procedure of Example42).

The oxyalkylatedresin was prepared so the final product represented .a50% solution in Xylene. The effectiveness of this oxyalkylated resin wasexamined by testing it in connection withanemulsion produced at the St.Gabriel field, St. Gabriel, Louisiana. The emulsion as produced was buffin color and contained approximately 70% to B. S. & W., equivalent to40% water. The oxyalkylated derivative above described was added to 100cc. of emulsion placed in 2a .150 cc. bottle. The amount added wasequivalent to :one part vof demulsifier in 25,000 parts or" emulsion.The mixture was shaken for three minutes in a shaking machine employing150 oscillations per minute. The emulsion began to change color at theend of one minute,-completelychanged color at the endof two minutes, andwas obviously breaking, evenduring the agitation period, by the end ofthe third minute. At theiendoften minutes of quiescentsettling, adistinct water layer had broken out. .Theemulsion was allowed tostandfor one hour at approximately to F. All the water was broken outwithin less than the hour, giving a clear separation. The gravity of therecovered oil was'34" A. P.'I., and the B. S. & W. content was less than0i 1%. In large scale use it'is not necessary to get a completeresolution within an hours time and the amount of demulsifier requiredwould be substantially less.

Example. 20

The demulsifier employed was the oxyalkyl'ated derivative of the resin'oflExample 3a prepared from para-tertiary amylphenol and formaldehyde,using an acid catalyst, oxyethylated with an amount of ethylene oxideequal in weight to the weight of the resin following the procedure ofExample b.

The oxyalkylated resin was prepared so the final product represented a50% solution in xylene. The effectiveness of this oxyalkylated resin wasexamined by testing it in connection with an emulsion produced at theSouth Houston field, South Houston, Texas. The emulsion as produced wasbrown in color and contained approximately '70% to 75% B. S. & W.,equivalent to 37% to 38% water. The oxyalkylated derivative abovedescribed was added to 100 cc. of emulsion placed in a 150 cc. bottle.The amount added was equivalent to one part of demulsifier in 25,000parts of emulsion. The mixture was shaken for three minutes in a shakingmachine employing 150 oscillations per minute. The emulsion began tochange color at the end of one minute, completely changed color at theend of two minutes and was obviously breaking, even during the agitationperiod, by the end of the third minute. At the end of ten minutes ofquiescent settling, a distinct water layer had broken out. The emulsionwas allowed to stand for one hour at approximately 90 to 100 F. All thewater was broken out within less than an hour, giving a clearseparation. The gravity of the recovered oil was 28 A. P. I., and the B.S. & W. content was less than of 1%.

Example 30 The demulsifier employed was the oxyalkylated derivative ofthe resin of Example 11a prepared from styrylphenol and formaldehyde,using an acid catalyst oxyethylated with an amount of ethylene oxideequal in weight to the weight of the resin, following the procedure ofExample 9?).

The oxyalkylated resin was prepared so the final product represented a50% solution in xylene. The effectiveness of this oxyalkylated resin wasexamined by testing it in connection with an emulsion produced at theHastings field, Hastings, Texas. The emulsion produced was buff in colorand contained approximately 65% to 70% B. S. & W., equivalent to 34%water. The oxyalkylated derivative above described was added to 100 cc.of emulsion placed in a 150 cc. bottle. The amount added was equivalentto one part of demulsifier in 25,000 parts of emulsion. The mixture wasshaken for three minutes in a shaking machine employing 150 oscillationsper minute. The emulsion began to change color at the end of one minute,completely changed color at the end of two minutes, and was obviouslybreaking, even during the agitation period, by the end of the thirdminute. At the end of ten minutes of quiescent settling, a distinctwater layer had broken out. The emulsion was allowed to stand for onehour at approximately 90 to 100 F. All the water was broken out withinless than an hour, giving a clear separation. The gravity of therecovered oil was 32 A. P. I., and the B. S. & W. content was less thanof 1%.

Actu .ly, in considering the ratio of alkylene oxide to add, and we havepreviously pointed out that this can be pre-determined using laboratorytests, it is our actual preference from a practical standpoint to maketests on a small pilot plantv scale. Our reason for so doing is that wemake one run, and only one, and that we have a complete series .whichshows the. progressive effect.

38 of introducing the oxyalkylating agent, for instance, the ethyleneoxyradicals. Our preferred procedure is as follows: We prepare a suitableresin, or for that matter, purchase it in the open market. We employ 8pounds of resin and 4 pounds of xylene and place the resin and xylene ina suitable autoclave with an open reflux condenser. We prefer to heatand stir until the solution is complete. We have pointed out that softresins which are fluid or semi-fluid can be readily prepared in variousways, such as the use of orthotertiary amylphenol,ortho-hydroxydiphenyl, or by the use of higher molecular weightaldehydes than formaldehyde. If such resins are used, a solvent need notbe added but may be added as a matter of convenience or for comparison,if

desired. We then add a catalyst, for instance, 2% of caustic soda, inthe form of a 20% to 30% solution, and remove the water of solution orformation. We then shut off the reflux condenser and use the equipmentas an autoclave only, and oxyethylate until a total of 60 pounds ofethylene oxide have been added, equivalent to 750% of the originalresin. We prefer a temperature of about C. to C. We also take samples atintermediate points as indicated in the following table:

Pounds of Ethylene Oxide Added per Percentage 8 pound BatchOxyethylation to 750% can usually be completed within 30 hours andfrequently more quickly.

The samples taken are rather small, for instance, 2 to 4 ounces, so thatno correction need be made in regard to the residual reaction mass. Eachsample is divided in two. One-half the sample is placed in anevaporating dish on the steam bath overnight so as to eliminate thexylene. Then 1.5% solutions are prepared from both series of samples, i.e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be sufiicient toindicate hydrophile character or surface activity, i. e., the product issoluble, forming a colloidal sol, or the aqueous solution foams or showsemulsifying property. All these properties are related throughadsorption at the interface, for example, a gas-liquid interface or aliquid-liquid interface. If desired, surface activity can be measured inany one of the usual ways using a Du Nouy tensiometer or droppingpipette, or any other procedure for measuring interfacial tension. Suchtests are conventional and require no further description. Any compoundhaving sub-surface-activity, and all derived from the same resin andoxyalkylated to a greater extent, 1. e., those having a greaterproportion of alkylene oxide, are useful for the practice of thisinvention.

Another reason why we prefer to use a pilot plant test of the kind abovedescribed is that we can use the same procedure to evaluate tolerancetowards a trifunctional phenol such as hydroxybenzene or metacresolsatisfactorily. Previous reference has been made to the fact that fillone can :conduct a laboratory scale test which will indicate whether:ornot a resin, although soluble insolvent, will yield an insolublerubbery product, i. e., a'product which is neither hydrophile norsuriace-iactive, upon oxyethylation, particularly extensiveoxyethylation. It is also oxvious that one may have a solvent-solubleresin derived from aimixture of phenols having present.1% or 2% ofatrifunctional phenol which will result in an insolublerubber at theultimate stages of oxyethylation but not in the earlier stages. In otherwords, with resins from some such phenols, addition of 2 or 3 moles ofthe oxyallcylating agent per phenolic nucleus, particularly ethyleneoxide, gives a surface-active product which is perfectly satisfactory,while more extensive oxyethylation yields'an insoluble rubber, that is,an unsuitable product. It is obvious that this present procedure ofevaluating trifunctional phenol tolerance is more suitable than .theprevious procedure.

It may be well to call attention to one result which may be noted in along drawn-out oxyalkylation, particularly oxyethylation, which wouldnot appear in a normally conducted reaction. Reference has been made tocross-linking and its effect on solubility and also the fact that, ifcarried farenough, it causes incipient stringiness, thenpronouncedstringiness, usually followed by a semi-rubbery or rubbery stage.Incipient stringiness, or even pronounced stringiness, or even thetendency toward a rubbery stage, is not objectionable so'long as thefinal product is still hydrophile and at least sub-surface-active. Suchmaterial frequently is best mixed with a polar solvent, such as alcoholor the like, and preferably an alcoholic solution is used. The pointwhich we want to make here, however, is this: Stringiness orrubberization at this stage may possibly be the result ofetherification. Obviously if a diiunctional phenol and an aldehydeproduce a non-cross linlred resin molecule and if such molecule isoxyallrylated so as to introduce a plurality of hydroxyl groups in eachmolecule, then and in that event if subsequent etherification takesplace, one is going to obtain crosslinking in the same general way thatone would obtain cross-linking inother resinification reactions.Ordinarilythere is little or no tendency toward etherification duringthe oxyalkylation step. If it does talze place at all, it is only to aninsignificant and undetectable degree. However, suppose that a'certainweight of resin is treated with an equal weight of, or twice its weightof, ethylene oxide. This may be done in a comparatively short time, forinstance, at 150 or 175 C. in 4 to8'hours, or even less. On theotherhand, if in an exploratory reaction, such-as the kind previouslyescribed, the ethylene oxide were added extremely slowly in order-totake stepwise samples, so that the reaction required 4 or 5 times aslong to introduce an equalamount of ethylene oxide employing the sametemperature, then etherification might cause stringiness or a suggestionotrubberiness. For this reason if in an exploratory experiment of thekind previously described there-appears to be-any stringiness orrubberiness, it may be well to repeat the "experiment and reach theintermediate ".stage of oxyalkylationas'rapidly as possible and thenproceed'slowly beyond this intermediate stage. The entire purpose ofthis modified procedure is to cut down the time of reaction so as toavoid etherification if it be caused by the extended time period.

:It may he 'well sto :note one peculiar :reaction sometimes noted in thecourse'ofoxyalkylation, particularly oxyethylationyoi the thermoplasticresins herein described. This efiect is noted a case where athermoplastic resinv has been'oxyallrylated, for instance,oxyethylated,'until-it gives a perfectly clear solutionyeven in thepresence of some accompanying water-insoluble solvent suchas 10%'to15%'-oi xylene. Further oxyalkyl'ation, particularly oxyethylation,may then yield a product which, instead of giving a clear solution aspreviously, gives a very milky solution suggesting that some markedchange has taken place. One explanation of the above change is thatthe-structural unit indicated in the following way where 81L isafairly'large number, for instance, 10 to 20, decomposes and anoxyalkylated resin representing a lower degree of oxyethylation andalesssoluble one, isgenerated and a cyclic polymer of ethylene oxide isproduced, indicated thus:

This fact, of course, presents no difiiculty for the reason thatoxyalkylation can be conducted in each instance stepwiseyor'at a gradualrate, and samples taken at short intervalsso as to ar-- rive atarpoint-where-optimum surface activityor hydrophile character isobtained if desired; for products'for use in-the practice of thisinvention, this is notnecessary and, in fact, may beundesirable, i. e.,reduce the efficiency of the product.

We do not know to what extent oxyalkylation produces uniformdistribution in regard to phenolic hydroxyls present in the resinmolecule. In some instances, of course, such distribution can not beuniform for the reason that we have not specified that the molecules ofethylene oxide, for example, be added in multiples of the units presentin the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum oftwo moles of ethylene oxide per phenolic nucleus are added, this wouldmean'an addition of 10 moles of ethylene oxide,

but suppose that one added 11 moles of ethylene oxide, or 12, or 13, or14 moles; obviously even assuming the most uniform distributionpossible, some of the polyethyleneoxy radicals would contain 3ethyleneoxy units and some would contain 2. Therefore, it :is impossibleto specify uniform distribution in regard to the entrance of theethylene oxide or other oxyallrylating agent. For that matter, if onewere 'tointroduce 25 moles of ethylene oxide there is no way to becertain'that all chains would have 5 units; there might be some having,for example 4 and 6 units, or. for that matter 3 or 'Tunits. -Nor isthere any basis forassuming that the number of molecules-of theoxyalkylatin'g agent added "to each of the :molecules of the :resin isthe same, or different. Thus, where formulae are given to

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING A HYDROPHILE OXYALKYLATED 2,4,6 C1- TO C24- HYDROCARBONSUBSTITUTED MONOCYCLIC PHENOLC1- TO C8- ALDEHYDE RESIN IN WHICH THERATIO OF OXYALKYLENE GROUPS TO PHENOLIC NUCLEI IS AT LEAST 2:1 AND THEALKYLENE RADICALS OF THE OXYALKYLENE GROUPS ARE SELECTED FROM THE GROUPCONSISTING OF ETHYLENE, PROPYLENE, BUTYLENE, HYDROXYPROPYLENE ANDHYROXYBUTYLENE RADICALS.